MOLTEN SALT BATTERY AND POWER SUPPLY SYSTEM
A material design of a molten salt battery which is suitable for a temperature range in which the battery is used is shown, and a molten salt battery applicable even under a severe environment where vibrations are given is provided. In the molten salt battery according to the present invention, the operating temperature range of 25° C. to 300° C. is divided into ranges of 25° C. to 120° C., 80° C. to 140° C. and 140° C. to 300° C., and for each temperature range, a material that is a choice is defined for each of an outer package, a binder, an anode active material and a separator as well as an electrolytic solution. Further, the molten salt battery includes a vibration controlling portion for reducing vibrations given to the outer package. As for the electrolytic solution, for example, an electrolytic solution containing an organic cation and FSA as an anion, or NaFSA is suitable for the range of 25° C. to 120° C., an electrolytic solution containing a mixture of NaFSA-KFSA is suitable for the range of 80° C. to 140° C., and an electrolytic solution containing a mixture of NaTFSA-CsTFSA is suitable for the range of 140° C. to 300° C.
Latest Sumitomo Electric Industries, Ltd. Patents:
The present invention relates to a molten salt battery using a molten salt as an electrolyte, and a power supply system including the molten salt battery.
BACKGROUND ARTRecently, as secondary batteries having, in addition to a high energy density, a potent advantage of incombustibility, molten salt batteries having a molten salt as an electrolyte have been developed and attracting attention (see Patent Literature 1 and Non-Patent Literature 1). Molten salt batteries can be operated over a temperature range of 57° C. to 190° C., a wider temperature range as compared to those for other secondary batteries such as lithium batteries. These molten salt batteries are expected to be applied to various applications.
CITATION LIST Patent LiteraturePatent Literature 1: Japanese Unexamined Patent Publication No. 2009-67644
Non-Patent LiteratureNon-Patent Literature 1: “SEI WORLD”, March 2011 (VOL. 402), Sumitomo Electric Industries, Ltd.
SUMMARY OF INVENTION Technical ProblemCurrently, however, material design intended for use at about 90° C. of the above-described temperature range is performed, and at present, no specific proposal has been presented yet as for a suitable material design in the case of use in different temperature ranges according to use purposes. Further, it is under consideration to considerably expand the temperature range over which the molten salt battery is operated.
The molten salt battery has such a feature that the operating temperature range is high as compared to those for other batteries such as lithium ion batteries, and the electrolyte is incombustible. Therefore, use of the molten salt battery under a severe environment such as a high-temperature environment or an environment under a load is explored.
In view of the problems described above, it is an object of the present invention to show a material design of a molten salt battery which is suitable for a temperature range in which the battery is used, and provide a molten salt battery applicable even under a severe environment, and a power supply system.
Solution to ProblemA molten salt battery of the present invention is a molten salt battery having an operating temperature range of 25° C. to 120° C., including:
an outer package formed of an aluminum plate, a stainless steel plate or a copper plate, or a multi-layer plate formed by providing any one of the plates with an insulating coating;
a cathode which has as a cathode material a material containing a cathode active material and using PVDF as a binder or using PTFE as a binder and which is stored in the outer package;
an anode which has an anode active material containing at least one of metal sodium, a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material and which is stored in the outer package;
a separator interposed between the cathode and the anode adjacent to each other and formed of a polyolefin-based material, PTFE, glass fibers or a ceramic;
an electrolytic solution with which the separator is impregnated and which contains an organic cation and FSA as an anion, or NaFSA; and
a vibration controlling portion for reducing vibrations given to the outer package.
A molten salt battery of the present invention is a molten salt battery having an operating temperature range of 80° C. to 140° C., including:
an outer package formed of an aluminum plate, a stainless steel plate or a copper plate, or a multi-layer plate formed by providing any one of the plates with an insulating coating;
a cathode which has as a cathode material a material containing a cathode active material and using PVDF as a binder or using PTFE as a binder and which is stored in the outer package;
an anode which has an anode active material containing at least one of metal sodium, a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material and which is stored in the outer package;
a separator interposed between the cathode and the anode adjacent to each other and formed of a polyolefin-based material, PTFE, glass fibers or a ceramic;
an electrolytic solution with which the separator is impregnated and which contains a mixture of NaFSA and KFSA; and
a vibration controlling portion for reducing vibrations given to the outer package.
A molten salt battery of the present invention is a molten salt battery having an operating temperature range of 140° C. to 300° C., including:
an outer package formed of an aluminum plate, a stainless steel plate or a copper plate;
a cathode which has as a cathode material a material containing a cathode active material and excluding a binder or using PTFE as a binder and which is stored in the outer package;
an anode which has an anode active material containing at least one of a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material and which is stored in the outer package;
a separator interposed between the cathode and the anode adjacent to each other and formed of PTFE, glass fibers or a ceramic;
an electrolytic solution with which the separator is impregnated and which contains a mixture of NaTFSA and TFSA; and
a vibration controlling portion for reducing vibrations given to the outer package.
A power supply system of the present invention includes:
any one of the foregoing molten salt batteries as a power supply; and
a charge-discharge mechanism for charging and discharging the molten salt battery.
A power supply system of the present invention includes:
any one of the above-mentioned molten salt batteries as a power supply;
a charge-discharge mechanism for charging and discharging the molten salt battery; and
-
- an energy conversion mechanism for converting kinetic energy of a fluid into electrical energy, and supplying the electrical energy to the charge-discharge mechanism.
A power supply system of the present invention includes:
any one of the foregoing molten salt batteries as a power supply; and
a sensor which is operated by power supplied from the molten salt battery.
A power supply system of the present invention includes:
any one of the foregoing molten salt batteries as a power supply; and
communication apparatus which is operated by power supplied from the molten salt battery.
Advantageous Effects of InventionAccording to a molten salt battery and a power supply system of the present invention, the molten salt battery can be formed from suitable materials appropriate to a temperature range in which the battery is used, and the molten salt battery can be used under a severe environment where vibrations are given.
<Subject Matters of Embodiments of the Invention>
First, subject matters of embodiments of the present invention will be listed and described. The embodiments described below can also be arbitrarily partially combined.
(1) A molten salt battery according to an embodiment of the present invention is a molten salt battery having an operating temperature range of 25° C. to 120° C., including:
an outer package formed of an aluminum plate, a stainless steel plate or a copper plate, or a multi-layer plate formed by providing any one of the plates with an insulating coating;
a cathode which has as a cathode material a material containing a cathode active material and using PVDF as a binder or using PTFE as a binder and which is stored in the outer package;
an anode which has an anode active material containing at least one of metal sodium, a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material and which is stored in the outer package;
a separator interposed between the cathode and the anode adjacent to each other and formed of a polyolefin-based material, PTFE, glass fibers or a ceramic;
an electrolytic solution with which the separator is impregnated and which contains an organic cation and FSA as an anion, or NaFSA; and
a vibration controlling portion for reducing vibrations given to the outer package.
A molten salt battery, the materials of which are selected in the manner described above, has improved performance as a battery (charge-discharge efficiency and cycle characteristics) over an operating temperature of 25° C. to 120° C. Further, the molten salt battery includes a vibration controlling portion for reducing vibrations given to the outer package, and therefore can be suitably used even under a severe environment where vibrations are given from outside.
(2) A molten salt battery according to another embodiment of the present invention is a molten salt battery having an operating temperature range of 80° C. to 140° C., including:
an outer package formed of an aluminum plate, a stainless steel plate or a copper plate, or a multi-layer plate formed by providing any one of the plates with an insulating coating;
a cathode which has as a cathode material a material containing a cathode active material and using PVDF as a binder or using PTFE as a binder and which is stored in the outer package;
an anode which has an anode active material containing at least one of metal sodium, a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material and which is stored in the outer package;
a separator interposed between the cathode and the anode adjacent to each other and formed of a polyolefin-based material, PTFE, glass fibers or a ceramic;
an electrolytic solution with which the separator is impregnated and which contains a mixture of NaFSA and KFSA; and
a vibration controlling portion for reducing vibrations given to the outer package.
A molten salt battery, the materials of which are selected in the manner described above, has improved performance as a battery (charge-discharge efficiency and cycle characteristics) over an operating temperature of 80° C. to 140° C. Further, the molten salt battery includes a vibration controlling portion for reducing vibrations given to the outer package, and therefore can be suitably used even under a severe environment where vibrations are given from outside.
(3) A molten salt battery according to still another embodiment of the present invention is a molten salt battery having an operating temperature range of 140° C. to 300° C., including:
an outer package formed of an aluminum plate, a stainless steel plate or a copper plate;
a cathode which has as a cathode material a material containing a cathode active material and excluding a binder or using PTFE as a binder and which is stored in the outer package;
an anode which has an anode active material containing at least one of a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material and which is stored in the outer package;
a separator interposed between the cathode and the anode adjacent to each other and formed of PTFE, glass fibers or a ceramic;
an electrolytic solution with which the separator is impregnated and which contains a mixture of NaTFSA and TFSA; and
a vibration controlling portion for reducing vibrations given to the outer package.
A molten salt battery, the materials of which are selected in the manner described above, has improved performance as a battery (charge-discharge efficiency and cycle characteristics) over an operating temperature of 140° C. to 300° C. Further, the molten salt battery includes a vibration controlling portion for reducing vibrations given to the outer package, and therefore can be suitably used even under a severe environment where vibrations are given from outside.
(4) The vibration controlling portion preferably includes a case for housing the outer package and vibration controlling member provided between the case and the outer package.
Owing to this configuration, vibrations given to the case can be suitably prevented from being transmitted to the outer package and internal components thereof.
(5) A power supply system according to an embodiment of the present invention includes:
the molten salt battery according to any one of (1) to (4) as a power supply; and
a charge-discharge mechanism for charging and discharging the molten salt battery.
By forming a molten salt battery and a charge-discharge mechanism as one system as described above, the molten salt battery can be suitably used under an environment where change of the battery is difficult or under an environment where long-term use is required.
(6) A power supply system according to another embodiment of the present invention includes:
the molten salt battery according to any one of (1) to (4) as a power supply;
a charge-discharge mechanism for charging and discharging the molten salt battery; and
an energy conversion mechanism for converting kinetic energy of a fluid into electrical energy, and supplying the electrical energy to the charge-discharge mechanism.
By forming a molten salt battery, a charge-discharge mechanism and an energy conversion mechanism as one system as described above, the molten salt battery can be suitably used under an environment where change of the battery is difficult or under an environment where long-term use is required.
(7) A power supply system according to still another embodiment of the present invention includes:
the molten salt battery according to any one of (1) to (4) as a power supply; and
a sensor which is operated by power supplied from the molten salt battery.
By forming a molten salt battery and a sensor as one system as described above, power can be suitably supplied to the sensor.
(8) A power supply system according to still another embodiment of the present invention includes:
the molten salt battery according to any one of (1) to (4) as a power supply; and
communication apparatus which is operated by power supplied from the molten salt battery.
By forming a molten salt battery and communication apparatus as one system as described above, power can be suitably supplied to the communication apparatus.
The molten salt batteries in (1) to (4), and the power supply systems formed by combination of the molten salt battery with a charge-discharge mechanism, an energy conversion mechanism, a sensor and communication apparatus in (5) to (8) can be suitably applied to devices that are used under a severe environment, such as an excavator for excavating a well in order to extract underground resources etc., and an inspection device for performing inspection (stratum inspection) of the inside of a well.
DETAILS OF EMBODIMENTS OF THE INVENTIONThe embodiments of the present invention will be described in detail below with reference to the drawings.
<<Basic Structure of Molten Salt Battery>>
First, the basic structure of the molten salt battery will be described.
A material of the cathode collector 1a is, for example, an aluminum nonwoven fabric (line diameter: 100 μm; porosity: 80%). The cathode material 1b includes a cathode active material and a binder in a kneaded form thereof. The cathode collector 1a that is an aluminum nonwoven fabric is filled with the resulting mixture, dried, and then pressed, for example, at 100 MPa to form the cathode 1 in a thickness of about 1 mm.
On the other hand, in the anode 2, an anode active material is formed in such a manner as to be deposited on the anode collector 2a made of aluminum.
The separator 3 interposed between the cathode 1 and the anode 2 is obtained by impregnating a material such as nonwoven fabric (thickness: 200 μm), which easily absorbs a liquid, with a molten salt as an electrolytic solution (electrolyte). At a temperature equal to or higher than the melting point, the molten salt is melted to contact the cathode 1 and the anode 2 in the form of an electrolytic solution L with ions dissolved therein at a high concentration. The molten salt is incombustible.
Next, a more specific configuration of the electric power generation element of the molten salt battery will be described below.
In
The separator 3 is interposed between the cathode 1 and the anode 2 adjacent to each other, and in other words, the cathodes 1 and the anodes 2 are alternately stacked with the separator 3 interposed between the cathode 1 and the anode 2. As the number of these components that are stacked in practice, for example, the number of cathodes 1 is 20, the number of anodes 2 is 21, and the number of separators 3 is 20 as “bags”, but the number of separators 3 each interposed between the cathode 1 and the anode 2 is 40. The separator 3 is not necessarily bag-shaped, and there may be 40 separated separators.
In
<<One Form of Molten Salt Battery>>
The molten salt battery body 10 configured as described above is housed in, for example, an outer package (battery container) which is made of an aluminum alloy and has rectangular parallelepiped shape, and forms a unit cell, i.e. a physical single body as a battery. Hereinafter, such a unit cell as a single body is given reference sign B and described as a “molten salt battery B”.
The single body shape of the molten salt battery B illustrated in
The molten salt battery B described above can be used in a state of an assembled battery configured such that a plurality of batteries are gathered together and connected in series or in series/parallel for obtaining a voltage and current capacity required for a use purpose.
<<Specific Materials Associated with Operating Temperature>>
Next, the cathode active material and the binder that form the cathode material 1b, the anode active material that forms the anode material 2b, the separator 3, the outer package 11 and the electrolytic solution L will be described for each operating temperature by showing specific examples.
First, for the separator, a PO (polyolefin)-based material (for example, polyethylene or polypropylene) can be used at 20° C. to 140° C. A porous body of PTFE (polytetrafluoroethylene) can be used at 20° C. to 250° C. Glass fibers or a ceramic can be used at 20° C. to a temperature higher than 300° C.
For the binder, PVDF (polyvinylidene fluoride) can be used at 20° C. to 140° C. PTFE can be used at 20° C. to 250° C. In the case of a binderless battery (no binder used), use at 20° C. to a temperature higher than 300° C. is possible. In the case of a binderless battery, a porous metal body should be used as a cathode collector.
For the electrolytic solution, one containing an organic cation and FSA (bisfluorosulfonylamide) as an anion, or NaFSA (sodium bisfluorosulfonylamide) can be used at 25° C. to 120° C. A mixture of NaFSA-KFSA (potassium bisfluorosulfonylamide) (molar ratio: 56:44) can be used at 80° C. to 140° C. The “mixture of NaFSA-KFSA” means a “mixture of NaFSA and KFSA”. Hereinafter, similarly the “-” (hyphen) is used. A mixture of NaTFSA (sodium bistrifluoromethylsulfonylamide)-CsTFSA (cesium bistrifluoromethylsulfonylamide) (molar ratio: 20:80) can be used at 140° C. to a temperature higher than 300° C.
Further, a mixture of NaFSA-KFSA-CsFSA shown in
As the organic cation, for example, alkyl imidazole-based cations such as a 1-ethyl-3-methylimidazolium cation, alkyl pyrrolidinium-based cations such as a N-ethyl-N-methylpyrrolidinium cation, alkyl pyridinium-based cations such as a 1-methyl-pyridinium cation and quaternary ammonium-based cations such as a trimethylhexyl ammonium cation can be used.
For the anode active material, metal sodium precipitated at the anode can be used at 20° C. to about 100° C. Sn (tin) or a tin-based material containing Sn can be used at about 90° C. to 220° C. A silicon-based material (e.g. Si, ZnSi or SiO2) can be used at 20° C. to 300° C. A carbon-based material (e.g. hard carbon) and a titanium oxide-based material (e.g. Na4Ti5O12 or Na3Ti5O7) can be used at 20° C. to 300° C.
For the outer package, a multi-layer plate formed by providing insulating coatings on both surfaces of an aluminum plate, a stainless steel plate or a copper plate can be used at 20° C. to about 120° C. Herein, the “plate” includes a foil. A metal plate which is not provided with an insulating coating (but insulation of the cathode/anode is secured) can be used at 20° C. to 300° C. However, a metal plate which is not provided with an insulating coating requires insulation to be secured in other structures, and therefore it may be preferred to use a multi-layer plate provided with an insulating coating where possible.
As the cathode active material, NaCrO2 or Na2/3(Fe1/3Mn2/3)O2 can be used at a temperature ranging from 20° C. to 300° C. although not shown in
If the above-described results are divided by temperature ranges centered on the electrolytic solution, it is preferred that they are divided by three ranges of 25° C. to 120° C., 80° C. to 140° C. and 140° C. to 300° C. Then, suitable materials for these three operating temperature ranges are summarized as follows.
<<Suitable Materials for Each Operating Temperature>>
(Operating Temperature: 25° C. To 120° C.)
[Outer Package]
Multi-layer plate formed by providing an insulating coating on an aluminum plate, a stainless steel plate or a copper plate
[Cathode]
Cathode active material: NaCrO2 or Na2/3(Fe1/3Mn2/3)O2
Binder: PVDF or PTFE
[Anode]
Anode active material: one containing at least one of metal sodium, a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material
[Separator]
Polyolefin-based material, PTFE, glass fibers or ceramic
[Electrolytic Solution]
Electrolytic solution containing an organic cation and FSA as an anion, or NaFSA
(Operating Temperature: 80° C. To 140° C.)
[Outer Package]
Multi-layer plate formed by providing an insulating coating on an aluminum plate, a stainless steel plate or a copper plate
[Cathode]
Cathode active material: NaCrO2 or Na2/3(Fe1/3Mn2/3)O2
Binder: PVDF or PTFE
[Anode]
Anode active material: one containing at least one of metal sodium, a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material
[Separator]
Polyolefin-based material, PTFE, glass fibers or ceramic
[Electrolytic Solution] Electrolytic solution containing a mixture of NaFSA-KFSA
(Operating Temperature: 140° C. To 300° C.)
[Outer Package]
Aluminum plate, stainless steel plate or copper plate
[Cathode]
Cathode active material: NaCrO2 or Na2/3(Fe1/3Mn2/3)O2
Binder: Binderless or PTFE
[Anode]
Anode active material: one containing at least one of a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material
[Separator]
PTFE, glass fibers or ceramic
[Electrolytic Solution]
Electrolytic solution containing a mixture of NaTFSA-CsTFSA
Next, an example of the result of a charge-discharge test when a cathode active material, a binder, an anode active material and an electrolytic solution are selected from the above-described suitable materials is shown.
The cathode material is a mixture of NaCrO2, Denka Black (carbon black) and PVDF in a weight ratio of 85:10:5. The anode material is a mixture of Na2Ti3O7, Denka Black and PVDF in a weight ratio of 80:15:5. The electrolytic solution (electrolyte) is a mixture of NaFSA and Py13FSA (N-methyl-N-propylpyrrolidinium FSA) in a molar ratio of 20:80.
In
The cathode material is a mixture of NaCrO2, Denka Black and PVDF in a weight ratio of 85:10:5. The anode material is a mixture of Na2Ti3O7, Denka Black and PVDF in a weight ratio of 80:15:5. The electrolytic solution (electrolyte) is a mixture of NaFSA and KFSA in a molar ratio of 56:44.
In
The cathode material is a mixture of NaCrO2, acetylene black and PTFE in a weight ratio of 85:10:5. As the anode material, hard carbon is used. The electrolytic solution (electrolyte) is a mixture of NaTFSA and Py13TFSA (N-methyl-N-propylpyrrolidinium TFSA) in a molar ratio of 10:90.
In
By selecting suitable materials for three operating temperature ranges as described above, there can be provided a molten salt battery excellent in performance as a battery (charge-discharge efficiency and cycle characteristics) over a wide temperature range of 25° C. to 300° C.
The example is illustrative, but it is considered that by selecting any materials from the above-described suitable materials for each operating temperature range, a similar result can be obtained.
<<Configuration of Molten Salt Battery Having Vibration Controlling Portion>>
The molten salt battery according to the present invention (molten salt battery described in claims) includes one or more molten salt batteries B described above and a vibration controlling portion 30 described below. The vibration controlling portion 30 reduces vibrations transmitted into the outer package 11 of the molten salt battery B, thereby preventing damage and the like of the molten salt battery B to enhance durability. In the foregoing descriptions, a unit cell in which the molten salt battery body 10 (electric power generation element) is housed in the outer package 11 is referred to as the “molten salt battery B”, but in the descriptions below, in addition thereto, a molten salt battery including the molten salt battery B and the vibration controlling portion 30 is given reference sign 100 and referred to as a “molten salt battery 100” (or a “molten salt assembled battery 100”).
The vibration controlling members 21 and 22 exhibit a vibration controlling effect of absorbing, within the case 20, vibrations given to the molten salt assembled battery 100 from outside, so that impacts on the molten salt batteries B are relieved. Therefore, it is possible to cope with use under an environment where strong vibrations are generated. Here, the case 20 and the vibration controlling members 21 and 22 constitute the vibration controlling portion 30 for reducing vibrations given to the molten salt battery B. Examples of use of the molten salt battery B under an environment where strong vibrations are generated include application to a well excavator as described later. In this case, the molten salt battery B can resist vibrations of 1 G or more, preferably 6 G or more, more preferably even 12 G.
In this embodiment, vibration resistance performance of the whole molten salt assembled battery 100 is enhanced, and therefore vibration resistance performance required for individual molten salt batteries B (e.g. material strength of the outer package 11, bonding strength, strength of the separator 3, etc.) can be reduced, thus making it possible to reduce costs.
The vibration controlling members 21 and 22 do not have to be provided everywhere between adjacent molten salt batteries B or between the inner surface of the case 20 and the molten salt batteries B, but may be provided at locations where the vibration controlling members are required to obtain a necessary vibration controlling effect. In the case 20, one (single) molten salt battery B may be housed rather than a plurality of molten salt batteries B. In this case, the vibration controlling members 21 and 22 may be provided between the inner surface of the case 20 and the molten salt battery B.
The vibration controlling members 21 and 22 may be configured as a rubber heater. In this case, by embedding a heat generator 21b (22b) in the vibration controlling member 21 (22) as illustrated in
When a plurality of molten salt batteries B are arranged, the vibration controlling members 21 and 22 as in the above-described embodiment are not held between adjacent molten salt batteries B, and the outer packages 11 may be brought into close contact with each other, or there may be a slight gap therebetween. A plurality of molten salt batteries B are supported by support members (vibration controlling means) 24 fixed so as to protrude from the inner surface (front surface, back surface, both left and right side surfaces and bottom surface) of the case 20. The support member 24 is composed of an elastic material such as a silicone rubber or a fluororubber like the above-described vibration controlling members 21 and 22, and has excellent elasticity for absorption of vibrations and impacts. In place of a rubber, for example, a coil spring can be used.
The case 20 is filled with an oil (vibration controlling means) 25 to such a level that the upper part of the molten salt battery B is not immersed in the oil 25. As the oil 25, a silicone oil or a fluorine-based oil is suitable, and one having sufficient viscosity, rather than fluent liquid quality, is suitable. Buoyancy of the oil 25 reduces a load applied to the support member 24 at the bottom surface. The support members 24 at the front surface, the back surface and both left and right side surfaces support the molten salt battery only to the extent that the posture of the outer package 11 is kept upright, and are therefore under a small load as compared to the support member 24 at the bottom surface.
In the molten salt assembled battery 100 illustrated in
In this embodiment, a heater 23 may be provided in the lower part in the case 20. When a current is passed through the heater 23, the oil 25 is heated, and the heated oil 25 serves as a heating medium to heat the outer packages 11, so that the electrolytes of the molten salt batteries B can be melted.
This embodiment is different from the above-described embodiment in the form of the case 20 and the support structure of the molten salt battery B to the case 20. Otherwise this embodiment is the same as the second embodiment, the same reference signs are given, and detailed descriptions are omitted.
In
Since the outer package 11 is not fixed to but suspended from the case 20 (lid 20b), vibrations of the case 20 are hard to be transmitted directly to the outer package 11, and vibrations of the outer package 11 are relieved due to viscosity of the oil 25. As described above, in this embodiment, the oil 25 principally has a function as the vibration controlling portion 30, and the suspension structure assists the function as the vibration controlling portion 30.
<<Use Mode of Molten Salt Battery 100>>
Next, one use mode of the molten salt battery having the vibration controlling portion 30 as described above will be described.
The well excavator 50 of this embodiment excavates a hole (well) under the ground for the purpose of extraction of underground resources or engineering works, and is particularly a rotary excavator which efficiently excavates a well of great depth to the existence stratum of underground fluid resources such as petroleum, natural gas or geothermal steam for extracting the resources.
The rotary excavator 50 includes a tower 52 built on a floor 51 installed on the land, a drill string (excavation tube) 54 supported in a suspended state by the tower 52 and provided at the lead end with a bit (excavation tool) 53 for crushing rock, a hoisting device 55 for elevating and lowering the drill string 54 in the vertical direction, a rotating device 56 for rotating the drill string 54, and a muddy water supplying device 58 for supplying muddy water as an excavation fluid into a well H.
The drill string 54 is composed of a series of pipes, and includes a kelly 59, a drill pipe 60 and a drill collar 61 in the descending order. The bit 53 is provided at the lower end of the drill collar 61.
The rotating device 56 includes a rotary joint 62 connected to the upper end of the drill string 54, and a rotating table 63 provided on the floor 51 to rotate the kelly 59 of the drill string 54 about the axial center in the vertical direction by a motor (not illustrated). Rotation of the drill string 54 causes the bit 53 to dig through the stratum.
The hoisting device 55 can elevate and lower the drill string 54 using a pulley 65 to adjust a load given to a bottom hole from the bit 53 at the lower end of the drill string 54.
The muddy water supplying device 58 delivers muddy water from a muddy water pump 66, causes the muddy water to flow into the drill string 54 through the rotary joint 62, and jets the muddy water to the bottom hole from the bit 53. The muddy water jetted from the bit 53 is caused to pass through a ring gap between the outside of the drill string 54 and the well H and return to the ground. In this way, cuttings crushed by the bit 53 can be discharged to the ground, while ingress of stratum fluids is prevented by controlling the pressure of the inside of the well H, friction of the drill string 54 is reduced, devices in the well are cooled, and so on.
The sensor 70 includes at least one of various kinds of sensors such as, for example, a sensor for measuring the temperature and pressure of the vicinity of the bottom hole, a sensor for measuring the direction, gradient, etc. of the well, a sensor for measuring the vibration, load, torque, etc. of the bit 53, a sensor for measuring stratum evaluation information (stratum gamma rays, stratum specific resistance, etc.), and a sensor for measuring the viscosity, pressure, etc. of fluids (excavation fluid, stratum fluid (oil/gas), etc.) flowing through the inside or the outside of the drill collar 61.
The transmitter-receiver 71 performs communication of information with a transmitter-receiver (not illustrated) installed on the ground, and is used, for example, for transmitting information detected by the above-described various kinds of sensors 70 and receiving various kinds of information (control information etc.) from the transmitter-receiver on the ground.
For the transmitter-receiver 71, the following systems are employed: a mud pulse system in which a pressure wave corresponding to information to be transmitted is generated in muddy water and propagated through the inside of the drill string 54; and an electromagnetic wave system in which information is transmitted and received through an electromagnetic wave.
Various kinds of sensors 70 and the transmitter-receiver 71 are operated by power supplied from the secondary battery 73. The secondary battery 73 is charged and discharged by the charge-discharge mechanism 72.
The charge-discharge mechanism 72 includes a charge-discharge circuit which performs control of the current and the voltage, management of the charge-discharge time, direct current-alternating current conversion, etc. for achieving a discharge function of supplying electrical energy (charges) stored in the secondary battery to devices such as the sensor 70 and the transmitter-receiver 71 and a charge function of storing electrical energy supplied from the energy conversion mechanism 74 in the secondary battery 73.
The energy conversion mechanism 74 includes a screw 75 rotatably supported in the drill collar 61, and a generator (electric power generator) 76 for converting rotating power (kinetic energy) of the screw 75 into electrical energy. The screw 75 is rotated by the flow of fluids flowing through the drill collar 61, for example, muddy water as an excavation fluid or fluids in the stratum (oil and gas), and the generator 76 is operated by the rotating power thereof to generate power, so that the secondary battery 73 can be charged through the charge-discharge mechanism 72.
Electrical devices such as the sensor 70 and the transmitter-receiver 71 may be configured to be supplied with electrical energy not only from the secondary battery 73 but also directly from the energy conversion mechanism 74 as necessary.
For the secondary battery 73 provided in the drill collar 61 of the excavator 50, the molten salt battery 100 described previously is used.
The secondary battery 73 to be used for the excavator 50 should resist a temperature of about 165° C. to 200° C., i.e. an environmental temperature during excavation. The molten salt battery 100 of the present invention can be used over a wide operating temperature range as described previously, and can be suitably applied to the drill string 54 of the excavator 50 because the highest operating temperature range is set to 140° C. to 300° C. The secondary battery 73 to be used for the excavator 50 is required to be capable of being used continuously for at least several weeks (e.g. 2 to 6 weeks). The molten salt battery 100 of the present invention has small self discharge even under a high-temperature environment, and can be charged by the charge-discharge mechanism 72, so that the requirement of continuous use over a predetermined period of time can be suitably met. The molten salt battery 100 does not catch fire or generate a combustible gas due to a reaction with a substance (water etc.) present around the well because an incombustible electrolyte is used.
The molten salt battery 100 includes the vibration controlling portion 30. Therefore, the molten salt battery 100 can be suitably used even under an environment where large vibrations associated with excavation of the well H are given. The molten salt battery 100 can be mounted on the outer surface or the inner surface of the drill string 54, or incorporated into the drill string 54. In any case, the molten salt battery can be formed into a shape compatible with the shape of the drill string 54, for example, a cylindrical shape or arc shape (C shape) which conforms to the cylindrical shape of the drill string 54.
The power supply system including various kinds of sensors 70, the transmitter-receiver 71, the charge-discharge mechanism 72, the energy conversion mechanism 74 and the secondary battery 73 can be applied to not only the drill string 54 in the course of excavation of the well H, but also various kinds of measurement devices and various kinds of tube members (extraction tube for circulating stratum fluids (production fluids) such as an oil and a gas, etc.) which are inserted into the well H in place of the drill string 54 after completion of excavation or in the course of the excavation process. For the secondary battery 73, various conditions as shown below are required according to situations of a well to which the battery is to be applied.
For example, as one operating condition of the secondary battery in the well, operations at a high temperature of 180° C. or higher, or about 225° C. in some cases, may be required. As described previously, the molten salt battery 100 (or B) of this embodiment can be used over a wide operating temperature range, and the highest operating temperature range is set to 140° C. to 300° C. When a molten salt battery having such an operating temperature range is used, the operating condition described above can be suitably met. A molten salt battery having the operating temperature range described above has small self discharge caused by heat, and can be charged by the charge-discharge mechanism 72, so that an operating period condition can be suitably satisfied.
As another operating condition of the secondary battery in the well, constant operations over a long period of time may be required although the operating temperature is not so high (e.g. 60° C. to 150° C.). The molten salt battery 100 of the present invention can be charged by the charge-discharge mechanism 72, so that the operating period condition can be suitably satisfied. The molten salt battery 100 (or B) of the present invention has an operating temperature range of 80° C. to 140° C. or 25° C. to 120° C. as described previously. Therefore, when a molten salt battery having either of the above-mentioned operating temperature ranges is used, the operating condition described above can also be met.
Embodiments that are disclosed herein should be considered illustrative, rather than limiting, in all respects. The scope of the present invention is defined by the appended claims, and all changes are intended to be included within descriptions and scopes equivalent to the appended claims.
The molten salt battery (and power supply system) according to the present invention can be applied to not only wells for extracting an oil or a gas from a conventional oil field or gas field, but also wells for extracting an oil or a gas from a non-conventional oil field or gas field such as an oil shale or an oil sand. The molten salt battery (and power supply system) can also be applied to wells for geothermal development.
The molten salt battery according to the present invention may supply power to devices other than sensors and communication apparatus, for example, solenoids (actuators) for manipulating various kinds of valves, and the power supply system according to the present invention may include devices other than sensors and communication apparatus. For example, the molten salt battery (or power supply system) may supply power to a sampling device for sampling stratum fluids. The molten salt battery (or power supply system) itself may be provided in a sampling device, or may supply power to sensors and communication apparatus, solenoids and the like which are provided in the sampling device.
For the molten salt battery in the embodiments described above, a molten salt principally including sodium ions as a cation is used, but a molten salt including lithium ions may be used.
REFERENCE SIGNS LIST
-
- 1: POSITIVE ELECTRODE
- 2: NEGATIVE ELECTRODE
- 3: SEPARATOR
- 20: CASE
- 21: VIBRATION CONTROLLING MEMBER (VIBRATION CONTROLLING MEANS)
- 24: SUPPORT MEMBER (VIBRATION CONTROLLING MEANS)
- 25: OIL (VIBRATION CONTROLLING MEANS)
- 70: SENSOR
- 71: TRANSMITTER-RECEIVER(COMMUNICATION MEANS)
- 72: CHARGE-DISCHARGE MECHANISM
- 73: SECONDARY BATTERY
- 100: MOLTEN SALT BATTERY (MOLTEN SALT ASSEMBLED BATTERY)
- B: MOLTEN SALT BATTERY
- L: ELECTROLYTIC SOLUTION
Claims
1. A molten salt battery having an operating temperature range of 25° C. to 120° C., comprising:
- an outer package formed of an aluminum plate, a stainless steel plate or a copper plate, or a multi-layer plate formed by providing any one of the plates with an insulating coating;
- a cathode which has as a cathode material a material containing a cathode active material and using PVDF as a binder or using PTFE as a binder and which is stored in the outer package;
- an anode which has an anode active material containing at least one of metal sodium, a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material and which is stored in the outer package;
- a separator interposed between the cathode and the anode adjacent to each other and formed of a polyolefin-based material, PTFE, glass fibers or a ceramic;
- an electrolytic solution with which the separator is impregnated and which contains an organic cation and FSA as an anion, or NaFSA; and
- a vibration controlling portion for reducing vibrations given to the outer package.
2. A molten salt battery having an operating temperature range of 80° C. to 140° C., comprising:
- an outer package formed of an aluminum plate, a stainless steel plate or a copper plate, or a multi-layer plate formed by providing any one of the plates with an insulating coating;
- a cathode which has as a cathode material a material containing a cathode active material and using PVDF as a binder or using PTFE as a binder and which is stored in the outer package;
- an anode which has an anode active material containing at least one of metal sodium, a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material and which is stored in the outer package;
- a separator interposed between the cathode and the anode adjacent to each other and formed of a polyolefin-based material, PTFE, glass fibers or a ceramic;
- an electrolytic solution with which the separator is impregnated and which contains a mixture of NaFSA and KFSA; and
- a vibration controlling portion for reducing vibrations given to the outer package.
3. A molten salt battery having an operating temperature range of 140° C. to 300° C., comprising:
- an outer package formed of an aluminum plate, a stainless steel plate or a copper plate;
- a cathode which has as a cathode material a material containing a cathode active material and excluding a binder or using PTFE as a binder and which is stored in the outer package;
- an anode which has an anode active material containing at least one of a tin-based material, a silicon-based material, a carbon-based material and a titanium oxide-based material and which is stored in the outer package;
- a separator interposed between the cathode and the anode adjacent to each other and formed of PTFE, glass fibers or a ceramic;
- an electrolytic solution with which the separator is impregnated and which contains a mixture of NaTFSA and TFSA; and
- a vibration controlling portion for reducing vibrations given to the outer package.
4. The molten salt battery according to claim 1, wherein the vibration controlling portion comprises a case for housing the outer package and vibration controlling means provided between the case and the outer package.
5. The molten salt battery according to claim 2, wherein the vibration controlling portion comprises a case for housing the outer package and vibration controlling means provided between the case and the outer package.
6. The molten salt battery according to claim 3, wherein the vibration controlling portion comprises a case for housing the outer package and vibration controlling means provided between the case and the outer package.
7. A power supply system, comprising:
- the molten salt battery according to claim 1 as a power supply; and
- a charge-discharge mechanism for charging and discharging the molten salt battery.
8. A power supply system, comprising:
- the molten salt battery according to claim 2 as a power supply; and
- a charge-discharge mechanism for charging and discharging the molten salt battery.
9. A power supply system, comprising:
- the molten salt battery according to claim 3 as a power supply; and
- a charge-discharge mechanism for charging and discharging the molten salt battery.
10. A power supply system, comprising:
- the molten salt battery according to claim 1 as a power supply;
- a charge-discharge mechanism for charging and discharging the molten salt battery; and
- an energy conversion mechanism for converting kinetic energy of a fluid into electrical energy, and supplying the electrical energy to the charge-discharge mechanism.
11. A power supply system, comprising:
- the molten salt battery according to claim 2 as a power supply;
- a charge-discharge mechanism for charging and discharging the molten salt battery; and
- an energy conversion mechanism for converting kinetic energy of a fluid into electrical energy, and supplying the electrical energy to the charge-discharge mechanism.
12. A power supply system, comprising:
- the molten salt battery according to claim 2 as a power supply;
- a charge-discharge mechanism for charging and discharging the molten salt battery; and
- an energy conversion mechanism for converting kinetic energy of a fluid into electrical energy, and supplying the electrical energy to the charge-discharge mechanism.
13. A power supply system, comprising:
- the molten salt battery according to claim 1 as a power supply; and
- a sensor which is operated by power supplied from the molten salt battery.
14. A power supply system, comprising:
- the molten salt battery according to claim 2 as a power supply; and
- a sensor which is operated by power supplied from the molten salt battery.
15. A power supply system, comprising:
- the molten salt battery according to claim 3 as a power supply; and
- a sensor which is operated by power supplied from the molten salt battery.
16. A power supply system, comprising:
- the molten salt battery according to claim 1 as a power supply; and
- communication apparatus which is operated by power supplied from the molten salt battery.
17. A power supply system, comprising:
- the molten salt battery according to claim 2 as a power supply; and
- communication apparatus which is operated by power supplied from the molten salt battery.
18. A power supply system, comprising:
- the molten salt battery according to claim 3 as a power supply; and
- communication apparatus which is operated by power supplied from the molten salt battery.
Type: Application
Filed: Nov 15, 2013
Publication Date: May 21, 2015
Applicant: Sumitomo Electric Industries, Ltd. (Osaka)
Inventors: Keiichiro TANABE (Osaka), Koma NUMATA (Osaka), Koji NITTA (Osaka), Shoichiro SAKAI (Osaka), Atsushi FUKUNAGA (Osaka), Eiko ITANI (Osaka), Shinji INAZAWA (Osaka)
Application Number: 14/081,632
International Classification: H01M 10/36 (20060101); H01M 2/02 (20060101); H01M 4/62 (20060101); H01M 2/16 (20060101); H01M 10/48 (20060101); H02J 7/00 (20060101);